CN108505137A - A kind of Thermotropic Liquid Crystalline Copolyesters fiber and preparation method thereof - Google Patents
A kind of Thermotropic Liquid Crystalline Copolyesters fiber and preparation method thereof Download PDFInfo
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- CN108505137A CN108505137A CN201810261002.4A CN201810261002A CN108505137A CN 108505137 A CN108505137 A CN 108505137A CN 201810261002 A CN201810261002 A CN 201810261002A CN 108505137 A CN108505137 A CN 108505137A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
Abstract
The invention discloses a kind of Thermotropic Liquid Crystalline Copolyesters fibers and preparation method thereof.The preparation method is that：Thermotropic Liquid Crystalline Copolyesters are sliced and are plasticized at 300~370 DEG C by single screw extrusion machine, nascent polyarylate fiber is obtained through metering pump-metered, filament spinning component spinning, drawing-off, receipts silk successively after exhaust；Under the nitrogen stream containing organic acid anhydride, nascent polyarylate fiber is subjected to 2 20h solid phases at 240~330 DEG C, obtains Thermotropic Liquid Crystalline Copolyesters fiber.The fracture strength of the Thermotropic Liquid Crystalline Copolyesters fiber of preparation is 4.6~6.5GPa.The preparation method of the high intensity thermotropic liquid crystal polyarylate fiber of the present invention is easy to operate, and process conditions are easily controllable, are convenient for continuous production, has broad application prospects and important economic value.
Description
Technical field
The present invention relates to a kind of high-performance thermotropic liquid-crystalline polymer fibers and preparation method thereof, belong to high-performance chemical fibre skill
Art field.
Background technology
Liquid crystal high polymer material (LCP) is a kind of new material developed the 1960s, is contained in strand rigid
Property rodlike or dish-shaped group, liquid crystalline phase can be formed under solution or molten condition, to impart this kind of material some solely
Special performance.LCP is under external force induction, and molecule can be height-oriented so that LCP shows excellent machinery, photoelectricity, thermal stability
Etc. performances.According to the condition of Formation of liquid crystals, liquid crystal polymer LCP can be divided into thermotropic liquid crystalline polymer and lyotropic liquid crystalline polymer again
Two major classes.The main representative of thermotropic liquid crystalline polymer is Thermotropic Liquid Crystalline Copolyesters.The Typical Representative of lyotropic liquid crystalline polymer is virtue
Fragrant polyamide is obtained by aromatic diacid and aromatic diamine polycondensation.The fifties to the seventies, DuPont Corporation's input are big
The research that manpower financial capacity carries out high molecule liquid crystal fermentation is measured, it is strong better than the superelevation of glass fibre, high that intensity was developed in 1972
ModulusFiber, and it is put to industrialization.Thermotropic liquid crystalline polymer is that ontology shows liquid crystal state in the molten state
One family macromolecule, compared with the lyotropic liquid crystalline polymer for showing liquid crystal state in the solution, processing method is simple and environmentally friendly.Heat
Cause liquid crystal polymer that can generally not involve using and recycling for solvent in process with melt spinning, injection molding and film forming,
It is the current one type of liquid crystal macromolecule for realizing that trade names are most in industrialized production.Such as CelaneseA Moke
Oil companyEastman KodakEqual thermotropic liquid crystalline polymers have captured the global markets LCP
Leading position.In addition, since most thermotropic liquid crystalline polymer TLCP products are polyarylate liquid crystal, traditionally thermotropic liquid
Polycrystalline macromolecule TLCP refers exclusively to polyarylate again, and thermotropic liquid crystalline polymer TLCP is also equal to polyarylate to a certain extent.
Polyarylate be it is a kind of macromolecule made of aromatic ring is connected by ester bond, molecular structure and a traditional random ball of string or
Cross-linked network structure is different, is made of long just rodlike molecular cell link.Liquid crystal is formed during heating.When it
When being cooled to solid-state from liquid crystal state, the height-oriented arrangement of strand can be retained, and form distinctive height-oriented knot
Structure, and make performance that there is anisotropy.Thermotropic liquid crystal polyarylate has high-strength and high-modulus, resistance to anti-flammability, low water absorption, good ruler
The series of advantages such as very little stability are widely used in the fields such as automobile, electronics, military project, protection.For synthesizing aromatic polyester liquid
There are many brilliant monomer, main to be segmented into 3 types according to the property that monomer functional is rolled into a ball：On aromatic ring one end be hydroxyl (H),
One end is that carboxylic acid group (A) is AH types, such as P-hydroxybenzoic acid (HBA), 2- hydroxyl -6- naphthoic acids (HNA)；Aromatic ring contains
2 carboxylic acid groups are AA types, such as terephthalic acid (TPA) (TPA), M-phthalic acid, biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid；On aromatic ring
It is HH types, such as hydroquinone (HQ), '-biphenyl diphenol (BP), 2,6- naphthalenediols etc. containing 2 hydroxyls.
When thermotropic liquid crystal polymer is pressed through spinneret orifice under shearing force, numberator height is orientated, due to
Slack time is long, and orientation texture is almost kept during cooling and solidifying, therefore, high property just can be obtained by melt spinning
It can thermotropic liquid crystal polyarylate fiber.But due to polymer raw, formula design, polymerization unit, spinning equipment, Equipment for Heating Processing etc.
The restriction of various aspects, really realizes industrialized, is closed by Celanese Corp. of the U.S. and Kuraray company in nineteen ninety
What work was developedFiber, Kuraray Xi Tiao factories start to produceFiber product.In April, 2005, Kuraray
The company merging high-performance fiber business of the Celanese advanced material company (CAMI) in South Carolina, USA state.Specifically simultaneously
Purchase is so that Kuraray group is unique as the worldThe source of fiber.Subsequent Kuraray further expands business and complete
Product sale is carried out on gauge ball mould.With the rapid growth of the market demand, Kuraray Corporation is to it in the western item in the counties Ai Ai within 2007
The process units in city carries out expanding energy, and production capacity increases 1000 tons from 600 tons.
The fracture strength of polyarylate fiber is generally in 3GPa or so, a little higher than aramid fiber (2.8GPa).Fiber one
As up to 3.3GPa (《Polyarylate fiber》, National Defense Industry Press, 2017, page 135；CN1252462A；US5945216).
Polyarylate fiber can be greatly improved fibrous fracture intensity, but its by E.I.Du Pont Company by being heat-treated to as-spun fibre
Intensity is also in 3GPa or so.Heilungkiang Ju Xiang Science and Technology Development Co., Ltd.s pass through P-hydroxybenzoic acid and 2- (4- hydroxy phenyls)-
5- carboxy benzimidazoles are copolymerized, and are prepared for the novel liquid crystal polyarylate that a kind of intensity is up to 4.0~4.5GPa
(CN201410612674.7).In recent years, right with the extension of polyarylate fiber application field and the progress of aeronautical and space technology
The intensity of polyarylate fiber proposes further requirement.Present invention innovation research by system provides a kind of fibrous fracture
Intensity is more than the high-performance Thermotropic Liquid Crystalline Copolyesters fiber and preparation method thereof of 4.6GPa.
Invention content
Problem to be solved by this invention is：A kind of high-performance thermotropic liquid crystal of the fibrous fracture intensity more than 4.6GPa is provided
Polyarylate fiber and preparation method thereof.
To solve the above-mentioned problems, the present invention provides a kind of preparation method of Thermotropic Liquid Crystalline Copolyesters fiber, features
It is, includes the following steps：
Step 1)：Thermotropic Liquid Crystalline Copolyesters are sliced and are plasticized at 300~370 DEG C by single screw extrusion machine, after exhaust
Successively nascent polyarylate fiber is obtained through metering pump-metered, filament spinning component spinning, drawing-off, receipts silk；
Step 2)：Under the nitrogen stream containing organic acid anhydride, nascent polyarylate fiber is subjected to 2-20h at 240~330 DEG C
Solid phase obtains Thermotropic Liquid Crystalline Copolyesters fiber.
Preferably, the Thermotropic Liquid Crystalline Copolyesters in the step 1) are P-hydroxybenzoic acid and 2- hydroxyl -6- naphthoic acids
Copolyesters.
Preferably, a concentration of 0.1~10 μm ol/L of the organic acid anhydride in the step 2) in nitrogen stream.
Preferably, the organic acid anhydride in the step 2) is acetic anhydride.
In as-spun fibre solid state polymerization processes of the present invention, depending on solid phase polymerization temperature is by the fusing point of Thermotropic Liquid Crystalline Copolyesters.
In view of temperature is too low, polymerization speed is slow；It is excessively high that adhesion, solid phase polymerization temperature can be caused generally to be set in polyarylate fusing point or less
10 DEG C -50 DEG C or so, between being typically in the range of 280-350 DEG C in view of high-performance polyarylate fusing point, plasticization temperature is generally set in 230
Between~340 DEG C.It is preferred that between 240~330 DEG C.When solid phase regarding target molecular weight and the type of Thermotropic Liquid Crystalline Copolyesters and
Fixed, in the present invention, since in the presence of acid anhydrides, polymerization speed is fast, it is fine that general 1-30h can obtain high molecular weight polyarylate
Dimension, preferably 2-20h.
The present invention provides a kind of thermotropic liquid crystal prepared by the preparation method using above-mentioned Thermotropic Liquid Crystalline Copolyesters fiber is poly-
Aromatic ester fiber, which is characterized in that the fracture strength of the fiber be 4.6~6.5GPa, preferably fracture strength be 5.0~
6.5GPa。
Preferably, it is 1g/L's by solvent compound concentration of the mixture of the Pentafluorophenol of isometric part and hexafluoroisopropanol
Polyarylate fiber solution, the logarithmic viscosity number IV at 25 DEG C are 10~50dL/g.
It is highly preferred that the logarithmic viscosity number IV is 30~50dL/g.The assay method of logarithmic viscosity number is：It will be hot
Liquid crystal polyarylate fiber is caused to be dissolved in Pentafluorophenol/hexafluoroisopropanol mixed solvent (the isometric part of Pentafluorophenol, hexafluoroisopropanol)
In, prepare the solution of 0.1g polyarylates/100ml mixed solvents, then measured in 25 DEG C using Ubbelohde viscometer and be computed and
.
There is the Thermotropic Liquid Crystalline Copolyesters fiber of the present invention excellent extension property, elongation at break to be generally higher than 4.0%,
It is preferably between 4.5~6.0%.Referring now to other known Thermotropic Liquid Crystalline Copolyesters fibers, high elongation at tear of the invention
Also high molecular weight is derived from.High intensity, which comes from the fiber, has high molecular weight, and high molecular weight derives from aforementioned nascent fibre
The solid phase of dimension.
The line density of the Thermotropic Liquid Crystalline Copolyesters fiber of the present invention there is larger impact, general line density to increase fibre strength
Greatly, fibre strength has a declining tendency.In order to ensure the high intensity of fiber, the line of the Thermotropic Liquid Crystalline Copolyesters fiber in the present invention
Density is typically in the range of between 3.00~6.00dtex；It is preferably between 3.00~4.00dtex.
Depending on single screw rod squeezes plasticization temperature by the property of Thermotropic Liquid Crystalline Copolyesters in above-mentioned preparation method, plasticization temperature is general
It is set in 20 DEG C or so of polyarylate fusing point or more, between being typically in the range of 280-350 DEG C in view of high-performance polyarylate fusing point, plasticizing temperature
Degree is generally set between 300~370 DEG C.On the one hand it considers mobility, on the other hand reduces thermal degradation, preferably 310 as possible
Between~350 DEG C.
The present invention does not have particular/special requirement to spun filament spinning speed, it is contemplated that production efficiency generally turns around speed and is set in
Between 200-2000 ms/min.The draw ratio of spinneret orifice is typically in the range of 1-15, preferably 4-10 in spinneret in the present invention.
The present invention improves the molecular weight of polyarylate fiber using solid phase.Solid phase is solid oligomer in height
In its glass transition temperature less than the polymerisation carried out under melting point polymer, this method can effectively improve polyester
The molecular weight of Type of Collective object.The mechanism of solid phase is：It is logical in the estrodur performed polymer (fiber, slice, powder etc.) of low molecular weight
It crosses crystallization and functional group's terminal groups, small molecule monomer and catalyst etc. is enriched in amorphous region, reaction is made to balance to positive direction
It is mobile；By decompression or inert gas reaction system small molecular by-product is taken away so that strand continues to increase, obtain compared with
The product of high molecular weight.For the solid phase of polyester simultaneously dependent on two aspects of chemical reaction and physical diffusion, process is reversible
Learn reaction, small molecule product diffuses to particle surface from inside particles and then diffuses into Decompression atmosphere from particle surface
Or atmosphere of inert gases.Determine that principle, the reaction rate of entire polymerisation are determined by an above-mentioned most slow step according to low speed.It is poly-
Time, polymerization temperature, catalyst, pressure or inert gas flow, performed polymer crystallinity, performed polymer geometry etc. are closed all by shadow
Ring the process of solid-phase polymerization.
In as-spun fibre solid state polymerization processes of the present invention, promotes polymerization speed using organic acid anhydride, improves extent of polymerization, with
Obtain high molecular weight polyarylate.There is no specifically limited for type of the present invention to acid anhydrides.In view of volatility and its in polyarylate
Diffusion velocity in fiber, generally preferably low carbon number fatty acid anhydride, the preferably acid anhydrides of the organic acid of C2-C6, most preferably acetic acid
Acid anhydride, propionic andydride and butyric anhydride.Organic acid anhydride content in nitrogen stream is typically in the range of between 0.01~100 μm of ol/L, preferably 0.1~
Between 10 μm of ol/L.
The type of polyarylate is not particularly limited in the present invention, can be that monomer is selected from P-hydroxybenzoic acid (HBA), 2-
Hydroxyl -6- naphthoic acids (HNA), terephthalic acid (TPA) (TPA), M-phthalic acid, biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, to benzene two
The arbitrary copolymer of phenol (HQ), '-biphenyl diphenol (BP), 2,6- naphthalenediols etc..It is preferred that by P-hydroxybenzoic acid (HBA), 2- hydroxyls
Base -6- naphthoic acids (HNA) copolymerization copolymerization polyarylate, by P-hydroxybenzoic acid (HBA), '-biphenyl diphenol (BP), benzene diformazan
The copolymerization polyarylate of acid copolymerization.Most preferably by P-hydroxybenzoic acid (HBA), 2- hydroxyl -6- naphthoic acids (HNA) copolymerization and
The copolymerization polyarylate come.
The preparation method of the high intensity thermotropic liquid crystal polyarylate fiber of the present invention is easy to operate, and process conditions are easily controllable,
It is convenient for continuous production, the drawing of finally obtained Thermotropic Liquid Crystalline Copolyesters fiber is stretched intensity up to 4.6~6.5GPa, had
Wide application prospect and important economic value.
Specific implementation mode
In order to make the present invention more obvious and understandable, it is hereby described in detail below with preferred embodiment.
The polyarylate used in embodiment 1-9 forA950 (HBA and HNA copolymers), Sumitomo Chemical
SUMIKASUPER LCP E6000 (HBA, BP and phthalic acid copolymer).
IV is logarithmic viscosity number in embodiment 1-9；Its unit dL/g is every gram of decilitre.
The measurement of IV：Polymer samples 0.2g is dissolved in the isometric part Pentafluorophenols of 200ml and hexafluoroisopropanol mixes
In solvent, it is configured to solution, is tested at 25 DEG C using Ubbelohde viscometer.
Embodiment 1
A950 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：260 DEG C of feed zone, 320 DEG C of melting zone, 315 DEG C of compressional zone, 315 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 260 are warming up to the heating rate of 1 DEG C/min
℃；At this point, importing acetic anhydride into nitrogen stream by syringe pump, the injection speed of acetic anhydride is 1 μ L/min；It is solid with this condition
Phase-polymerization 10 hours；High intensity thermotropic liquid crystal polyarylate fiber is obtained, fibrous fracture intensity is 4.8GPa, and elongation is
4.8%, IV 15dL/g.
Embodiment 2
A950 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：260 DEG C of feed zone, 320 DEG C of melting zone, 315 DEG C of compressional zone, 315 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 260 are warming up to the heating rate of 1 DEG C/min
℃；At this point, importing acetic anhydride into nitrogen stream by syringe pump, the injection speed of acetic anhydride is 10 μ L/min；With this condition
Solid phase 20 hours；High intensity thermotropic liquid crystal polyarylate fiber is obtained, fibrous fracture intensity is 6.3GPa, and elongation is
4.7%, IV 41dL/g.
Embodiment 3
A950 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：260 DEG C of feed zone, 320 DEG C of melting zone, 315 DEG C of compressional zone, 315 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 240 are warming up to the heating rate of 1 DEG C/min
℃；At this point, importing acetic anhydride into nitrogen stream by syringe pump, the injection speed of acetic anhydride is 10 μ L/min；With this condition
Solid phase 20 hours；High intensity thermotropic liquid crystal polyarylate fiber is obtained, fibrous fracture intensity is 4.9GPa, and elongation is
5.3%, IV 18dL/g.
Embodiment 4
A950 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：260 DEG C of feed zone, 320 DEG C of melting zone, 315 DEG C of compressional zone, 315 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 270 are warming up to the heating rate of 1 DEG C/min
℃；At this point, importing acetic anhydride into nitrogen stream by syringe pump, the injection speed of acetic anhydride is 80 μ L/min；With this condition
Solid phase 6 hours；High intensity thermotropic liquid crystal polyarylate fiber is obtained, fibrous fracture intensity is 5.5GPa, and elongation is
5.4%, IV 25dL/g.
Embodiment 5
A950 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：260 DEG C of feed zone, 320 DEG C of melting zone, 315 DEG C of compressional zone, 315 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 260 are warming up to the heating rate of 1 DEG C/min
℃；At this point, importing propionic andydride into nitrogen stream by syringe pump, the injection speed of propionic andydride is 10 μ L/min；With this condition
Solid phase 20 hours；High intensity thermotropic liquid crystal polyarylate fiber is obtained, fibrous fracture intensity is 5.9GPa, and elongation is
4.5%, IV 38dL/g.
Embodiment 6
A950 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：260 DEG C of feed zone, 320 DEG C of melting zone, 315 DEG C of compressional zone, 315 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 260 are warming up to the heating rate of 1 DEG C/min
℃；At this point, importing butyric anhydride into nitrogen stream by syringe pump, the injection speed of butyric anhydride is 10 μ L/min；With this condition
Solid phase 20 hours；High intensity thermotropic liquid crystal polyarylate fiber is obtained, fibrous fracture intensity is 5.6GPa, and elongation is
4.2%, IV 36dL/g.
Embodiment 7
E6000 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：330 DEG C of feed zone, 350 DEG C of melting zone, 350 DEG C of compressional zone, 350 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 320 are warming up to the heating rate of 1 DEG C/min
℃；At this point, importing acetic anhydride into nitrogen stream by syringe pump, the injection speed of acetic anhydride is 10 μ L/min；With this condition
Solid phase 15 hours；High intensity thermotropic liquid crystal polyarylate fiber is obtained, fibrous fracture intensity is 6.4GPa, and elongation is
5.5%, IV 38dL/g.
Embodiment 8
A950 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：260 DEG C of feed zone, 320 DEG C of melting zone, 315 DEG C of compressional zone, 315 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 260 are warming up to the heating rate of 1 DEG C/min
℃；At this point, importing acetic anhydride into nitrogen stream by syringe pump, the injection speed of acetic anhydride is 0.5 μ L/min；With this condition
Solid phase 10 hours；High intensity thermotropic liquid crystal polyarylate fiber is obtained, fibrous fracture intensity is 4.6GPa, and elongation is
4.6%, IV 12dL/g.
Embodiment 9
A950 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：260 DEG C of feed zone, 320 DEG C of melting zone, 315 DEG C of compressional zone, 315 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 270 are warming up to the heating rate of 1 DEG C/min
℃；At this point, importing acetic anhydride into nitrogen stream by syringe pump, the injection speed of acetic anhydride is 250 μ L/min；With this condition
Solid phase 6 hours；High intensity thermotropic liquid crystal polyarylate fiber is obtained, fibrous fracture intensity is 5.3GPa, and elongation is
5.1%, IV 23dL/g.
Comparative example 1
A950 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：260 DEG C of feed zone, 320 DEG C of melting zone, 315 DEG C of compressional zone, 315 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 260 are warming up to the heating rate of 1 DEG C/min
℃；Solid phase 20 hours under conditions of not importing organic acid anhydride；Obtain high intensity thermotropic liquid crystal polyarylate fiber, fiber
Fracture strength is 3.3GPa, elongation 3.2%, IV 9.5dL/g.
Comparative example 2
E6000 is dried under vacuum to moisture content at 120 DEG C and is less than 12ppm, then carries out melt spinning.Melt spinning
Screw rod heating temperature is respectively：330 DEG C of feed zone, 350 DEG C of melting zone, 350 DEG C of compressional zone, 350 DEG C of spin manifold temperature turn around speed
800m/min obtains as-spun fibre after spinning moulding.Solid phase then is carried out to as-spun fibre：By as-spun fibre as solid phase
It polymerize in case, after displacement nitrogen 3 times, adjustings nitrogen stream flow is 10L/min, and 320 are warming up to the heating rate of 1 DEG C/min
℃；Solid phase 15 hours under conditions of not importing organic acid anhydride；Obtain high intensity thermotropic liquid crystal polyarylate fiber, fiber
Fracture strength is 3.5GPa, elongation 3.5%, IV 8dL/g.
Claims (10)
1. a kind of preparation method of Thermotropic Liquid Crystalline Copolyesters fiber, which is characterized in that include the following steps：
Step 1)：Thermotropic Liquid Crystalline Copolyesters are sliced and are plasticized at 300~370 DEG C by single screw extrusion machine, after exhaust successively
Nascent polyarylate fiber is obtained through metering pump-metered, filament spinning component spinning, drawing-off, receipts silk；
Step 2)：Under the nitrogen stream containing organic acid anhydride, nascent polyarylate fiber is subjected to 2-20h solid phases at 240~330 DEG C
Polymerization, obtains Thermotropic Liquid Crystalline Copolyesters fiber.
2. the preparation method of Thermotropic Liquid Crystalline Copolyesters fiber as described in claim 1, which is characterized in that in the step 1)
Thermotropic Liquid Crystalline Copolyesters are the copolyesters of P-hydroxybenzoic acid and 2- hydroxyl -6- naphthoic acids.
3. the preparation method of Thermotropic Liquid Crystalline Copolyesters fiber as described in claim 1, which is characterized in that in the step 2)
A concentration of 0.1~10 μm ol/L of the organic acid anhydride in nitrogen stream.
4. the preparation method of Thermotropic Liquid Crystalline Copolyesters fiber as described in claim 1, which is characterized in that in the step 2)
Organic acid anhydride is acetic anhydride.
5. a kind of preparation method using the Thermotropic Liquid Crystalline Copolyesters fiber described in claim 1-4 any one is prepared thermotropic
Liquid crystal polyarylate fiber, which is characterized in that the fracture strength of the fiber is 4.6~6.5GPa.
6. Thermotropic Liquid Crystalline Copolyesters fiber as claimed in claim 5, which is characterized in that with the Pentafluorophenol of isometric part and six
The mixture of fluorine isopropanol is the polyarylate fiber solution that solvent compound concentration is 1g/L, the logarithmic viscosity number at 25 DEG C
IV is 10~50dL/g.
7. Thermotropic Liquid Crystalline Copolyesters fiber as claimed in claim 6, which is characterized in that the logarithmic viscosity number IV be 30~
50dL/g。
8. Thermotropic Liquid Crystalline Copolyesters fiber as claimed in claim 5, which is characterized in that the elongation at break of the fiber is
4.5~6.0%.
9. Thermotropic Liquid Crystalline Copolyesters fiber as claimed in claim 5, which is characterized in that the line density of the fiber be 3.00~
6.00dtex。
10. Thermotropic Liquid Crystalline Copolyesters fiber as claimed in claim 8, which is characterized in that the line density of the fiber is 3.00
~4.00dtex, fracture strength are 5.0~6.5GPa.
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| CN109930270A (en) * | 2019-03-08 | 2019-06-25 | 东华大学 | A kind of production method of the mixed yarn containing fire-retardant polyester fibre and polyarylate fiber |
| CN111072936A (en) * | 2019-12-23 | 2020-04-28 | 上海普利特化工新材料有限公司 | Wholly aromatic liquid crystal polyester resin and application thereof |
| CN111186112A (en) * | 2018-11-14 | 2020-05-22 | 宁波聚嘉新材料科技有限公司 | Preparation method of novel thermotropic liquid crystal high-performance polyarylate film |
| CN113103710A (en) * | 2021-04-02 | 2021-07-13 | 宁波聚嘉新材料科技有限公司 | LCP composite film suitable for high frequency and high speed and preparation method thereof |
| CN113698642A (en) * | 2021-09-29 | 2021-11-26 | 宁夏清研高分子新材料有限公司 | High-strength liquid crystal polymer film and preparation method thereof |
| CN117661139A (en) * | 2024-02-02 | 2024-03-08 | 烟台泰和新材高分子新材料研究院有限公司 | Preparation method of liquid crystal polyester fiber |
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| CN111186112A (en) * | 2018-11-14 | 2020-05-22 | 宁波聚嘉新材料科技有限公司 | Preparation method of novel thermotropic liquid crystal high-performance polyarylate film |
| CN109930270A (en) * | 2019-03-08 | 2019-06-25 | 东华大学 | A kind of production method of the mixed yarn containing fire-retardant polyester fibre and polyarylate fiber |
| CN109930270B (en) * | 2019-03-08 | 2020-06-12 | 东华大学 | Production method of blended yarn containing flame-retardant polyester fibers and polyarylate fibers |
| CN111072936A (en) * | 2019-12-23 | 2020-04-28 | 上海普利特化工新材料有限公司 | Wholly aromatic liquid crystal polyester resin and application thereof |
| CN113103710A (en) * | 2021-04-02 | 2021-07-13 | 宁波聚嘉新材料科技有限公司 | LCP composite film suitable for high frequency and high speed and preparation method thereof |
| CN113103710B (en) * | 2021-04-02 | 2022-01-07 | 宁波聚嘉新材料科技有限公司 | LCP composite film suitable for high frequency and high speed and preparation method thereof |
| CN113698642A (en) * | 2021-09-29 | 2021-11-26 | 宁夏清研高分子新材料有限公司 | High-strength liquid crystal polymer film and preparation method thereof |
| CN117661139A (en) * | 2024-02-02 | 2024-03-08 | 烟台泰和新材高分子新材料研究院有限公司 | Preparation method of liquid crystal polyester fiber |
| CN117661139B (en) * | 2024-02-02 | 2024-05-07 | 烟台泰和新材高分子新材料研究院有限公司 | Preparation method of liquid crystal polyester fiber |
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Application publication date: 20180907 Assignee: ZHEJIANG HAILIDE NEW MATERIAL Co.,Ltd. Assignor: DONGHUA University Contract record no.: X2022310000178 Denomination of invention: A thermotropic liquid crystalline polyarylester fiber and its preparation method Granted publication date: 20200811 License type: Exclusive License Record date: 20221219 |